Plastic material

ABSTRACT

A material comprising the reaction product of an A-side having a prepolymer isocyanate, preferably a prepolymer diisocyanate and a B-side having a cross-linker comprising a multifunction alcohol, a first vegetable oil, preferably a blown/oxidized vegetable oil, most preferably a blown/oxidized soybean oil, and a catalyst, wherein the first vegetable oil and the cross-linking agent are substantially non-esterfied prior to combining the A-side with the B-side and the method of producing the same.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of and claims the benefit of U.S. patentapplication Ser. No. 10/253,252, filed on Sep. 24, 2002 now U.S. Pat.No. 6,624,244, which is a continuation of Ser. No. 09/646,356, filedSep. 14, 2002 now U.S. Pat. No. 6,465,569, which is based upon andclaims the benefit of PCT Application No. PCT/US99/21511 filed on Sep.17, 1999, which is a continuation-in-part and claims the benefit of U.S.patent application Ser. No. 09/154,340, filed Sep. 17, 1998 which hasnow issued as U.S. Pat. No. 6,180,686.

BACKGROUND OF THE INVENTION

Because of their widely ranging mechanical properties and their abilityto be relatively easily machined and formed, plastic foams andelastomers have found wide use in a multitude of industrial and consumerapplications. In particular, urethane foams and elastomers have beenfound to be well suited for many applications. Automobiles, forinstance, contain a number of components, such as cabin interior parts,that are comprised of urethane foams and elastomers. Such urethane foamsare typically categorized as flexible, semi-rigid, or rigid foams withflexible foams generally being softer, less dense, more pliable, andmore subject to structural rebound subsequent to loading than rigidfoams.

The production of urethane foams and elastomers are well known in theart. Urethanes are formed when isocyanate (NCO) groups react withhydroxyl (OH) groups. The most common method of urethane production isvia the reaction of a polyol and an isocyanate which forms the backboneurethane group. A cross-linking agent may also be added. Depending onthe desired qualities of the final urethane product, the preciseformulation may be varied. Variables in the formulation include the typeand amounts of each of the reactants.

In the case of a urethane foam, a blowing agent is added to cause gas orvapor to be evolved during the reaction. The blowing agent creates thevoid cells in the final foam, and commonly is a solvent with arelatively low boiling point or water. A low boiling solvent evaporatesas heat is produced during the exothermic isocyanate/polyol reaction toform vapor bubbles. If water is used as a blowing agent, a reactionoccurs between the water and the isocyanate group to form an amine andcarbon dioxide (CO₂) gas in the form of bubbles. In either case, as thereaction proceeds and the material solidifies, the vapor or gas bubblesare locked into place to form void cells. Final urethane foam densityand rigidity may be controlled by varying the amount or type of blowingagent used.

A cross-linking agent is often used to promote chemical cross-linking toresult in a structured final urethane product. The particular type andamount of cross-linking agent used will determine final urethaneproperties such as elongation, tensile strength, tightness of cellstructure, tear resistance, and hardness. Generally, the degree ofcross-linking that occurs correlates to the flexibility of the finalfoam product. Relatively low molecular weight compounds with greaterthan single functionality are found to be useful as cross-linkingagents.

Catalysts may also be added to control reaction times and to effectfinal product qualities. The effects of catalysts generally include thespeed of the reaction. In this respect, the catalyst interplays with theblowing agent to effect the final product density. The reaction shouldproceed at a rate such that maximum gas or vapor evolution coincideswith the hardening of the reaction mass. Also, the effect of a catalystmay include a faster curing time so that a urethane foam may be producedin a matter of minutes instead of hours.

Polyols used in the production of urethanes are petrochemicals.Polyester polyols and polyether polyols being the most common polyolsused in urethanes production. For rigid foams, polyester or polyetherpolyols with molecular weights greater than 6,000, are generally used.For semi-rigid foams, polyester or polyether polyols with molecularweights of 3,000 to 6,000 are generally used, while for flexible foams,shorter chain polyols with molecular weight of 600 to 4,000 aregenerally used. There is a very wide variety of polyester and polyetherpolyols available for use, with particular polyols being used toengineer and produce a particular urethane elastomer or foam havingdesired particular final toughness, durability, density, flexibility,compression set ratios and modulus, and hardness qualities. Generally,higher molecular weight polyols and lower functionality polyols tend toproduce more flexible foams than do lighter polyols and higherfunctionality polyols. In order to eliminate the need to produce, store,and use different polyols, it would be advantageous to have a singleversatile component that was capable of being used to create finalurethane foams of widely varying qualities.

Further, use of petrochemicals such as polyester or polyether polyols isdisadvantageous for a variety of reasons. As petrochemicals areultimately derived from petroleum, they are a non-renewable resource.The production of a polyol requires a great deal of energy, as oil mustbe drilled, extracted from the ground, transported to refineries,refined, and otherwise processed to yield the polyol. These requiredefforts add to the cost of polyols and to the disadvantageousenvironmental effects of its production. Also, the price of polyolstends to be somewhat unpredictable as it tends to fluctuate based on thefluctuating price of petroleum.

Also, as the consuming public becomes more aware of environmentalissues, there are distinct marketing disadvantages topetrochemical-based products. Consumer demand for “greener” productscontinues to grow. As a result, it would be most advantageous to replacepolyester or polyether polyols, as used in the production of urethaneelastomers and foams, with a more versatile, renewable, less costly, andmore environmentally friendly component.

Efforts have been made to accomplish this. Plastics and foams made usingfatty acid triglycerides derived from vegetables have been developed,including soybeans derivatives. Because soybeans are a renewable,relatively inexpensive, versatile, and environmentally friendly, theyare desirable as ingredients for plastics manufacture. Soybeans may beprocessed to yield fatty acid triglyceride rich soy oil and protein richsoy flour.

Unlike urethanes, many plastics are protein based. For these types ofplastics, soy protein based formulations have been developed. U.S. Pat.No. 5,710,190, for instance, discloses the use of soy protein in thepreparation of a thermoplastic foam. Such plastics, however, are notsuitable for use in applications that call for the particular propertiesof urethanes. Since urethanes don't utilize proteins in theirformulations, soy proteins are not relevant to the manufacture ofurethanes.

Epoxidized soy oils, in combination with polyols, have also been used toformulate plastics and plastic foams, including urethanes. For example,U.S. Pat. No. 5,482,980 teaches using an epoxidized soy oil incombination with a polyol to produce a urethane foam. A polyester orpolyether polyol remains in the formulation, however. Also, as theepoxidation processing of the soy oil requires energy, material andtime, use of an unmodified soy oil would be more advantageous.

Efforts have been made to produce a urethane type cellular plastic fromun-modified soy oil. U.S. Pat. Nos. 2,787,601 and 2,833,730 disclose arigid cellular plastic material that may be prepared using any ofseveral vegetable oils, including soy oil as a prepolymer componentonly. The foam disclosed in these patents is made from a multistepprocess requiring the initial preparation of a prepolymer. Moreover, inthe case of U.S. Pat. No. 2,833,730, relatively low cross-linkerconcentrations are urged, resulting in questionable product stability.Further, use of a particular isocyanate, namely toluene diisocyanate, isdisclosed, which is disadvantageous due to its relatively high toxicity.

An unresolved need therefore exists in industry for a urethaneelastomer, a urethane foam, and a method of producing such materialsthat are based on a reaction between isocyanates alone or as aprepolymer, in combination with, a vegetable oil or a vegetableoil-polyurea polyol blend, are particularly desirable because they arerelatively inexpensive, versatile, renewable, environmentally friendlymaterial such as vegetable oils as a replacement for polyether orpolyester polyols typically employed.

SUMMARY OF THE INVENTION

One embodiment of the present invention includes a material thatincludes the reaction product of an A-side including a prepolymerisocyanate, preferably a prepolymer diisocyanate, and a B-side includinga vegetable oil, a cross-linking agent having a multi-functionalalcohol, and a catalyst that is substantially non-esterified.

Yet another embodiment of the present invention further includes amethod for preparing a material including the steps of combining anA-side including a prepolymer isocyanate, preferably a prepolymerdiisocyanate, and a B-side including a vegetable oil, a cross-linkingagent having a multi-functional alcohol, and a catalyst that issubstantially non-esterified.

These and other features, advantages and objects of the presentinvention will be further understood and appreciated by those skilled inthe art by reference to the following specification and claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The preparation of urethanes is well known in the art. They aregenerally produced by the reaction of petro-chemical polyols, eitherpolyester or polyether, with isocyanates. The flexibility or rigidity ofthe foam is dependent on the molecular weight and functionality of thepolyol and isocyanate used.

Petrochemical polyol-based polyurethanes can be prepared in a one stepor a two step process. In the one step process, what is known in the artas an A-side reactant is combined with what is known as a B-sidereactant. The A-side is generally considered to comprise an isocyanateor a mixture of diisocyanate. The diisocyanates typically used arediphenylmethane diisocyanate (MDI) or toluylenediisocyanate (TDI). Theparticular isocyanate chosen will depend on the particular finalqualities desired in the urethane.

The B-side material is generally a solution of a petroleum-basedpolyester or polyether polyol, cross-linking agent, and blowing agent. Acatalyst is also generally added to the B-side to control reaction speedand effect final product qualities. As discussed infra, the use of apetrochemical such as a polyester or polyether polyol is undesirable fora number of reasons.

It has been discovered, however, that flexible urethane foams of a highquality can be prepared by substituting the petroleum-based polyol inthe B-side preparation with a vegetable oil in the presence of amulti-functional alcohol cross-linking agent. The molar ratio of thehydroxyl (OH) groups of the cross-linking agent hydroxyl (OH) groups tothe vegetable oil is preferably at least 0.7:1, and most preferablybetween about 0.7 and 1.2:1. The replacement is made on a substantially1:1 weight ratio of vegetable oil for replaced petroleum-based polyol.Alternatively, a blend of petroleum-based polyol and vegetable oil maybe used. The process of producing the urethane does not changesignificantly with the petroleum-based polyol replaced by the vegetableoil with all other components and general methods as are generally knownin the art. The qualities of the final flexible, semi-rigid, or rigidurethane foam produced using the vegetable oil are consistent with thoseproduced using a high grade, expensive polyol.

Further, using a single vegetable oil, urethane foams of varying andselectable final qualities, including differing flexibility, density,and hardness, can be made by varying only the primary reactants. Itwould be difficult, if not impossible, to create such varied final foamsusing a single petroleum-based polyester or polyether polyol with thesame variations in the remaining reactants. Instead, differentpetroleum-based polyols would be required to produce such variedresults.

The use of vegetable oil in the urethane forming reaction also realizesa significant cost savings. Vegetable oils are abundant, renewable, andeasily processed commodities, as opposed to polyols, which petroleumderivatives and which entail significant associated processing costs. Assuch, they may currently be acquired for a cost of approximately halfthat of average grade petroleum-based polyurea, polyester or polyetherpolyols, and approximately one quarter the cost of high gradepetroleum-based polyester or polyether polyols. Also, as polyols derivedfrom petroleum, they are not renewable and carry a certain environmentalcost with them. There is a distinct marketing advantage to marketingproducts that are based on environmentally friendly, renewable resourcessuch as vegetable oils.

The A-side isocyanate reactant of the urethane of the invention ispreferably comprised of an isocyanate chosen from a number of suitableisocyanates as are generally known in the art. Different isocyanates maybe selected to create different properties in the final product. TheA-side reactant of the urethane of the invention comprises diisocyanate;4,4′ diphenylmethane diisocyanate; 2,4-diphenylmethane diisocyanate; andmodified diphenylmethane diisocyanate. Preferably, a modifieddiphenylmethane diisocyanate is used. It should be understood thatmixtures of different isocyanates may also be used.

The A-side of the reaction may also be a prepolymer isocyanate. Theprepolymer isocyanate is typically the reaction product of anisocyanate, preferably a diisocyanate, and most preferably some form ofdiphenylmethane diisocyanate and a vegetable oil. The vegetable oil canbe soy oil, rapeseed oil, cottonseed oil, or palm oil, or any other oilhaving a suitable number of reactive hydroxyl (OH) groups. The mostpreferred vegetable oil is soy oil. To create the prepolymerdiisocyanate, the vegetable oil and isocyanate are mixed in a 1:1 ratiofor 10-15 seconds every 10-15 minutes for a total of 4 hours or untilthe reaction has ended. There will still be unreacted isocyanate (NCO)groups in the prepolymer. However, the total amount of active A-sidematerial has increased through this process. The prepolymer reactionreduces the cost of the A-side component by decreasing the amount ofisocyanate required and utilizes a greater amount of inexpensive,environmentally friendly soy oil. In order to permit the prepolymerdiisocyanate A-side to react with the B-side, additional isocyanate mustbe added to elevate the isocyanate (NCO) level to an acceptable level.

The B-side reactant of the urethane reaction includes at least vegetableoil and a cross-linking agent. Typically, a blowing agent and a catalystare also included in the B-side. It is believed that the isocyanatereacts with the fatty acids of the vegetable oil to produce thepolymeric backbone of the urethane.

The vegetable oils that are suitable for use tend to be those that arerelatively high in triglyceride concentration and that are available ata relatively low cost. The preferred vegetable oil is soy oil, althoughit is contemplated that other vegetable oils, such as rapeseed oil (alsoknown as canola oil), cottonseed oil, and palm oil can be used inaccordance with the present invention. Except for the preliminaryblowing step where air is passed through the oil to remove impuritiesand to thicken it, the soy oil is otherwise unmodified. It does notrequire esterification as is required for some urethane products of theprior art. The preferred blown soy oil has the following composition:

100% Pure Soybean Oil Air Oxidized Moisture 1.15% Free Fatty Acid 5.92%as OLEIC Phosphorous 55.5 ppm Peroxide Value 137.22 Meq/Kg Iron 6.5 ppmHydroxyl Number 212 mg KOH/g Acid Value 12.46 mg KOH/g Sulfur 200 ppmTin <.5 ppm

Except for the use of the preferred unmodified, blown soy oil replacingthe polyol, the preferred B-side reactants used to produce the foam ofthe invention are generally known in the art. Accordingly, preferredblowing agents for the invention are those that are likewise known inthe art and may be chosen from the group comprising 134A HCFC, ahydrochloroflurocarbon refrigerant available from Dow Chemical Co.,Midland Mich.; methyl isobutyl ketone (MIBK); acetone; ahydroflurocarbon; and methylene chloride. These preferred blowing agentscreate vapor bubbles in the reacting mass. Should other blowing agentsbe used that react chemically, such as water reacting with theisocyanate (NCO) groups, to produce a gaseous product, concentrations ofother reactants may be adjusted to accommodate the reaction.

The cross-linking agents of the foam of the present invention are alsothose that are well known in the art. They must be at leastdi-functional (a diol). The preferred cross-linking agents for the foamof the invention are ethylene glycol and 1,4 butanediol; however, otherdiols may be used. It has been found that a mixture of ethylene glycoland 1,4 butanediol is particularly advantageous in the practice of thepresent invention. Ethylene glycol tends to offer a shorter chainmolecular structure with many “dead end” sites, tending to create afirmer final foam resistant to tearing or “unzipping,” while 1,4butanediol offers a longer chain molecular structure, tending to createa softer foam. Proper mixture of the two can create engineered foams ofalmost any desired structural characteristics.

In addition to the B-side's soy oil and blowing agent, one or morecatalyst may be present. The preferred catalysts for the urethanes ofthe present invention are those that are generally known in the art andare most preferably tertiary amines chosen from the group comprisingDABCO 33-LV® comprised of 33% 1,4 diaza-bicyclco-octane(triethylenediamine) and 67% dipropylene glycol, a gel catalystavailable from the Air Products Corporation; DABCO® BL-22 blowingcatalyst available from the Air Products Corporation; and POLYCAT® 41trimerization catalyst available from the Air Products Corporation.

Also as known in the art, the B-side reactant may further comprise asilicone surfactant which functions to influence liquid surface tensionand thereby influence the size of the bubbles formed and ultimately thesize of the hardened void cells in the final foam product. This caneffect foam density and foam rebound (index of elasticity of foam).Also, the surfactant may function as a cell opening agent to causelarger cells to be formed in the foam. This results in uniform foamdensity, increased rebound, and a softer foam.

A molecular sieve may further be present to absorb excess water from thereaction mixture. The preferred molecular sieve of the present inventionis available under the trade name L-paste™.

The flexible and semi-rigid foams of the invention will have greaterthan approximately 60% open cells. The preferred flexible foam of theinvention will also have a density of from 1 lb. to 45 lb. per cubicfoot and a hardness of durometer between 20 and 70 Shore “A.”

The urethane foam of the present invention is produced by combining theA-side reactant with the B-side reactant in the same manner as isgenerally known in the art. Advantageously, use of the vegetable oil toreplace the petroleum-based polyol does not require significant changesin the method of performing the reaction procedure. Upon combination ofthe A and B side reactants, an exothermic reaction ensues that may reachcompletion in anywhere from several minutes to several hours dependingon the particular reactants and concentrations used. Typically, thereaction is carried out in a mold so that the foam expands to fill themold, thereby creating a final foam product in the shape of the mold.

The components may be combined in differing amounts to yield differingresults, as will be shown in the Examples presented in the detaileddescription below. Generally, however, the preferred flexible foam ofthe invention B-side mixture, when using the preferred components, isprepared with the following general weight ratios:

Blown soy oil 100 parts Cross-linking agent 8-15 parts Blowing agent8-15 parts Catalyst 1-12 parts

A petroleum based polyol such as polyether polyol, polyester polyol, orpolyurea polyol may be substituted for some of the blown soy oil in theB-side of the reaction, however, this is not necessary. This preferredB-side formulation is then combined with the A-side to produce a foam.The preferred A-side, as discussed previously, is comprised of MDI or aprepolymer comprised of MDI and a vegetable oil, preferably soy oil. TheA-side and B-side are typically, and preferably in an approximate ratioof about 35 parts to about 85 parts A-side to 100 parts B-side.

Flexible urethane foams may be produced with differing final qualitiesusing the same vegetable oil by varying the particular other reactantschosen. For instance, it is expected that the use of relatively highmolecular weight and high functionality isocyanates will result in aless flexible foam than will use of a lower molecular weight and lowerfunctionality isocyanate when used with the same vegetable oil.Similarly, it is expected that lower molecular weight and lowerfunctionality cross-linkers will result in a more flexible foam thanwill higher molecular weight and higher functionality cross-linkers whenused with the same vegetable oil. Also, a ethylene glycol cross-linkerwill result in shorter final chains and a firmer foam, while use of abutanediol cross-linker results in longer chains and a softer foam.Moreover, it has been contemplated that chain extenders may also beemployed in the present invention. Butanediol, in addition to acting asa cross-linker, may act as a chain extender.

Urethane elastomers can be produced in much the same manner as urethanefoams, except that a blowing agent is not present to create void cellsin the material. It has been discovered that useful urethane elastomersmay be prepared using a vegetable oil to replace a petroleum-basedpolyester or polyether polyol. The preferred elastomer of the inventionis produced using diphenylmethane diisocyanate (MDI); 1,4 butanediolcross-linking agent; and a vegetable oil, preferably soy oil. A catalystmay be added to the reaction composition to decelerate the speed of thereaction. The preferred elastomer of the invention is prepared bycombining the reactants. An exothermic reaction occurs that creates theelastomer. The preferred elastomer has an approximate density of 65 lb.to 75 lb. per cubic foot.

The following examples of preparation of foams and elastomers of theinvention summarized in Table A will illustrate various embodiments ofthe invention. In the Examples, the B-Side (soy oil and othercomponents), once blended, has a shelf life of several months. TheA-side material in the following examples is comprised of modifieddiphenylmethane diisocyanate (MDI). The prepolymer A-side material inthe following examples is the reaction product of a vegetable oil,preferably soy oil, and a modified diphenylmethane diisocyanate (MDI).There are four different MDI materials specified in the followingexamples; all are modified monomeric or polymeric diphenylmethanediisocyanates available from the Bayer Corp., Polymers Division,Rosemont Ill.: “Mondur® MA-2901” (Bayer Product Code No. C-1464);“Mondur®-448”(Bayer Product Code No. G448), “Mondur® MRS-20”, and “Mondur®-PF”.

Also, “cure” in the following examples refers to the final, cured foamtaken from the mold. The soy oil used in the following examples is blownsoy oil obtained from Cargill, in Chicago, Ill. Catalysts used include“DABCO 33-LV®,” comprised of 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol available from the Air Products Urethanes Division;“DABCO® BL-22,” a tertiary amine blowing catalyst also available fromthe Air Products Urethanes Division; and “POLYCAT® 41” (n, n′, n″,dimethylamino-propyl-hexahydrotriazine tertiary amine) also availablefrom the Air Products Urethanes Division.

Catalysts in the following Examples may be referred to as “front end,”“back end,” and “blowing”. Front end catalysts tend to speed the earlyportion of the reaction, while back end catalysts tend to speed thelater, curing portion of the reaction. A blowing catalyst effects thetiming of the activation of the blowing agent. Some of the Examplesinclude “L-paste™,” which is a trade name for a molecular sieve forabsorbing water. Some also contain “DABCO® DC-5160,” a siliconesurfactant available from Air Products Urethane Division.

EXAMPLES Example 1

The B-side material was prepared as follows: 50 g Soy Oil 5 g EthyleneGlycol (cross-linker) 1 g Front end catalyst (DABCO 33-LV ®; 33%triethylenediamine and 67% dipropylene glycol) 1 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst) 4 g Methyl Isobutyl Ketone(blowing agent)

Blown soy oil has a molecular weight of about 278, while the ethyleneglycol has a molecular weight of about 62. Thus, the molar ratio ofethylene glycol to blown soy oil is 0.22:1. Since the ethylene glycolhas two hydroxyl (OH) groups with which to cross-link the constituentfatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH)groups of the ethylene glycol to soy oil is about 0.45:1. The resultingB-side was then combined with an A-side material in a ratio of 50 partsA-side to 100 parts B-side. The A-side material is comprised of Mondur®448, a modified monomeric diphenylmethane diisocyanate (pMDI). The curewas acceptable; however, the cellular material remained tacky at thesurface for 20 minutes.

Example 2

The B-side is the same as that of Example 1. The A-side is comprised ofMA-2901, a modified diphenylmethane diisocyanate. The B-side wascombined with the A-side in a ratio of 52 parts A-side to 100 partsB-side. The cure was acceptable, although the cellular material remainedtacky for 12 minutes.

Example 3

The A-side was the same as Example 2. The B-side was again the same asthat of Example 1, except that 1.5 parts of methanol were added asadditional blowing agent. The ratio was 52 parts A-side to 100 partsB-side. The sample cured in 1 hour. It was not a favorable result inthat the cellular material foamed and then fell back to solid and roseagain. The methanol apparently had an adverse affect.

Example 4

B-side: 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 2.5 g Front endcatalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 4 g Methyl Isobutyl Ketone (MIBK)

The A-side was the same as Example 2. The materials were reacted in aratio of 50 parts A-side to 100 parts B-side. The results were a goodfoam, but weak in tensile strength.

Example 5

The B-side and A-side are the same as in Example 4. However, thematerials were reacted in a ratio of 52 parts A-side to 100 partsB-side. The results were essentially the same as in Example 4 with alittle better tensile strength.

Example 6

B-side: 103 g Soy Oil 10 g Ethylene Glycol (cross-linker) 11 g Acetone(Blowing agent) 2.5 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst)

The molar ratio of ethylene glycol to blown soy oil is 0.44:1. With twohydroxyl (OH) groups with which to cross-link the constituent fattyacids of the blown soy oil, the molar ratio of the hydroxyl (OH) groupsof the ethylene glycol to soy oil is about 0.90:1. The A-side comprises52 parts MA-2901, a modified monomeric diphenylmethane diisocyanate, to100 parts B-side. The resulting foam was hard and its cell size large.It fell back to a solid, largely due to too much blowing agent.

Example 7

B-side: 100 g Soy Oil 8 g Ethylene Glycol (cross-linker) 5 g Acetone(Blowing agent) 2.5 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst)

The molar ratio of ethylene glycol to blown soy oil is 0.35 to 1. Withtwo hydroxyl (OH) groups with which to cross-link the constituent fattyacids of the blown soy oil, the molar ratio of the hydroxyl (OH) groupsof the ethylene glycol to soy oil is about 0.70:1. The A-side comprisesMA-2901, a modified monomeric diphenylmethane diisocyanate, and ispresent in 51 parts A-side to 100 parts B-side. The resulting foam isgenerally a good foam, having low tensile strength but a better densityrange.

Example 8

The B-side is the same as that of Example 7. The A-side also comprisesMA-2901, a modified monomeric diphenylmethane diisocyanate, as inExample 7. The A-side is present in a ratio of 45 parts A-side to 100parts B-side.

Example 9

The A-side and B-side are the same as in Example 7. However, 72 partsA-side were reacted with 100 parts B-side. The resulting foam fell backand did not cure after 1 hour, indicating an overcharge of A-side.

Example 10

B-side: 100 g Soy Oil 11 g Ethylene Glycol (cross-linker) 4 g MethylIsobutyl Ketone (MIBK) 3 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 3 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst)

The molar ratio of ethylene glycol to blown soy oil is 0.49:1. With twohydroxyl (OH) groups with which to cross-link the constituent fattyacids of the blown soy oil, the molar ratio of the hydroxyl (OH) groupsof the ethylene glycol to soy oil is about 0.99:1. The A-side comprisedMA-2901, a modified monomeric diphenylmethane diisocyanate. The A-sidewas reacted with the B-side in a ratio of 50 parts A-side to 100 partsB-side. The resulting foam had a 15-minute cure and a very slowrecovery. However, the final cure was insufficient because it did notoccur for 72 hours.

Example 11

B-side: 100 g Soy Oil 11 g Ethylene Glycol (cross-linker) 4 g MethylIsobutyl Ketone (MIBK) 3 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 3 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst)

The B-side is as in Example 10. The A-side comprises Mondur® 448, amodified monomeric diphenylmethane diisocyanate, in a ratio of 50 partsA-side to 100 parts B-side. The resulting foam cures in 15 minutes, butis very crumbly.

Example 12

B-side: 100 g Soy Oil 11 g Ethylene Glycol (cross-linker) 4 g MethylIsobutyl Ketone (MIBK) 3 g front end catalyst DABCO 33-LV ®; 33%diaza-bicyclo-octane and 67% dipropylene glycol) 3 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst)

The B-side is as in Example 10. The A-side comprised 76 parts MA-2901, amodified monomeric diphenylmethane diisocyanate, to 100 parts B-side.The resulting foam cures in 30 minutes, but has a very fast, completefall back.

Example 13

B-side: 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 5 g 1,4butanediol (cross-linker) 4 g Methyl Isobutyl Ketone (MIBK) 2.5 g Frontend catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst)

Ethylene glycol has a molecular weight of about 62 and 1,4 butanediolhas a molecular weight of about 90. Thus, the molar ratio of theethylene glycol to blown soy oil is 0.22:1 and the molar ratio of the1,4 butanediol to blown soy oil is 0.15:1. Since each of the ethyleneglycol and 1,4 butanediol have two hydroxyl (OH) groups with which tocross-link the constituent fatty acids of the blown soy oil, the molarratio of the hydroxyl (OH) groups of the 50/50 ethylene glycol/1,4butanediol cross-linker mixture to the blown soy oil is about 0.75:1.The A-side was reacted at 74 parts MA-2901, a modified monomericdiphenylmethane diisocyanate to 100 parts B-side. The resulting foamcured to the touch within 3 minutes and fully cured within 15 minutes.It has good properties.

Example 14

B-side: 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 5 g 1,4butanediol (cross-linker) 4 g Methyl Isobutyl Ketone (MIBK) 2.5 g Frontend catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Back end catalyst (POLYCAT ® 41; n, n′, n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 2 g Blowcatalyst (DABCO ® BL-22; a tertiary amine catalyst)

The A-side was reacted at 74 parts, a modified MDI, MA-2901, to 100parts B-side. The resulting foam cured to the touch within 3 minutes andexhibited slightly better initial strength than the foam of Example 13.It fully cured within 15 minutes with good properties.

Example 15

B-side: 200 g Soy Oil 7 g Ethylene Glycol (cross-linker) 16 g 1,4butanediol (cross linker) 2.5 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst) 2 g Back end catalyst(POLYCAT ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazinetertiary amine)

The molar ratio of the ethylene glycol to blown soy oil is 0.15:1 andthe molar ratio of the 1,4 butanediol to blown soy oil is 0.24:1. Sinceeach of the ethylene glycol and 1,4 butanediol have two hydroxyl (OH)groups with which to cross-link the constituent fatty acids of the blownsoy oil, the molar ratio of the hydroxyl (OH) groups of the 50/50ethylene glycol/1,4 butanediol cross-linker mixture to blown soy oil isabout 0.80:1.

The A-side was reacted at 74 parts, a modified MDI, MA-2901 to 100 partsB-side. The resulting foam had very good qualities. The foam exhibitedgood elastomeric and fast cure (tack-free after 90 seconds) propertiesand was soft with good elastomeric properties after 1 hour.

Example 16

The B-side is the same blend as Example 15. The A-side comprises, amodified MDI, Mondur® 448. The A-side was reacted at 74 parts A-side to100 parts B-side. The reaction time was good and the resulting foam wasa stiff flexible foam with good elastomeric properties. The foamcontinued to exhibit good elastomeric properties after 1 hour.

Example 17

B-side: 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 5 g 1,4butanediol (cross-linker) 2.5 g Front end catalyst DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst) 2 g Back end catalyst(POLYCAT ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazinetertiary amine) 2 g Molecular sieve (L-paste ™)

The molar ratio of the hydroxyl (OH) groups of the 50/50 ethyleneglycol/1,4 butanediol cross-linker mixture to soy oil is again about0.75:1.

The A-side comprises a 50/50 blend of, a modified MDI, MA-2901 and amodified pMDI, Mondur® 448. The A-side was reacted with the B-side at 74parts A-side to 100 parts B-side. The resulting foam is a good foam withgood flexibility, high density, but still needs tensile improvements.

Example 18

B-side: 200 g Soy Oil 5 g Ethylene Glycol (cross-linker) 21 g 1,4butanediol (cross-linker) 5 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 5 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst) 2 g Back end catalystPOLYCAT ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazinetertiary amine) 6 g Molecular sieve (L-paste ™)

The molar ratio of the hydroxyl (OH) groups of the 5/21 ethyleneglycol/1,4 butanediol mixture to blown soy oil is about 0.85:1.

The A-side comprises a 50/50 blend of a modified MDI, MA-2901 and amodified pMDI, Mondur® 448. The A-side was reacted with the B-side at 74parts A-side to 100 parts B-side. The resulting foam is very similar tothat of Example 17 and is a good foam with good flexibility, highdensity, but still needs tensile improvements.

Example 19

B-side: 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4butanediol (cross-linker) 2.5 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst) 5 g Back end catalyst(POLYCAT 41 ®; n, n′, n″, dimethylamino-propyl- hexahydrotriazinetertiary amine) 16 g Molecular sieve (L-paste ™) 4 g Siliconesurfactants (DABCO ® DC-5160)

The molar ratio of the hydroxyl (OH) groups of the 22/4 ethyleneglycol/1,4 butanediol mixture to blown soy oil is about 1.10:1. TheA-side comprises a modified MDI, MA-290. The A-side and the B-side werereacted at 74 parts A-side to 100 parts B-side. The resulting foamdemonstrated very good properties. It is almost a solid elastomer withgood rebound.

Example 20

B-side: 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4butanediol (cross-linker) 10 g Methylene Chloride (blowing agent) 2.5 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 5 g Back end catalyst (POLYCAT ® 41; n, n′, n″,dimethylamine-propyl- hexahydrotriazine tertiary amine) 16 g Molecularsieve (L-paste ™) 4 g Silicone surfactants (DABCO ® DC-5160)

The molar ratio of the hydroxyl (OH) groups of the 22/4 ethyleneglycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1.The A-side comprises a modified MDI, MA-2901, and was reacted at 74parts A-side to 100 parts B-side. The resulting foam was a very goodfoam having uniform cell size, good flex, moderate density, good reboundand higher tensile strength.

Example 21

B-side 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4butanediol (cross-linker) 10 g Methylene Chloride (blowing agent) 2.5 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 5 g Back end catalyst (POLYCAT 41 ®; n, n′, n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 16 g Molecularsieve (L-paste ™) 4 g Silicone surfactants (DABCO ® DC-5160) 2 g Greenpigment

The molar ratio of the hydroxyl (OH) groups of the 22/4 ethyleneglycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1.The A-side comprises a modified MDI, MA-2901, and was reacted at 81parts A-side to 100 parts B-side.

Example 22

B-side 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4butanediol (cross-linker) 12 g Methylene Chloride (blowing agent 2.5 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 5 g Back end catalyst POLYCAT 41 ®; n, n′, n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 16 g Molecularsieve (L-paste ™) 4 g Silicone surfactants (DABCO ® DC-5160) 2 g Greenpigment

The molar ratio of the hydroxyl (OH) groups of the 22/4 ethyleneglycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1.The A-side comprises a modified MDI, MA-2901. The A-side and the B-sidewere reacted at 80 parts A-side to 100 parts B-side. The resulting foamwas a good foam. It was a stiffer flexible foam with good cell size,good uniformity, and low to moderate density.

Example 23

B-side 400 g Soy Oil 35 g Ethylene Glycol (cross-linker) 15 g 1,4butanediol (cross-linker) 24 g Methylene Chloride (blowing agent) 5 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 9 g Back end catalyst (POLYCAT ® 41; n, n′, n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 32 g Molecularsieve (L-paste ™) 12.5 g Silicone surfactants (DABCO ® DC-5160) 4 gGreen pigment

The molar ratio of the hydroxyl (OH) groups of the 35/15 ethyleneglycol/1,4 butanediol mixture to blown soy oil is about 1.00:1. TheA-side comprises a modified MDI, MA-2901, and was reacted at 74 partsA-side to 100 parts B-side. The resulting foam is low in density withpoor tensile strength.

Example 24

B-side 235 g Soy Oil 25 g Ethylene Glycol (cross-linker) 6 g 1,4butanediol (cross-linker) 12 g Methylene Chloride (blowing agent) 2 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 1.75 g Back end catalyst (POLYCAT 41 ®; n, n′, n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 25 g Molecularsieve (L-paste ™)

The molar ratio of the hydroxyl (OH) groups of the 25/6 ethyleneglycol/1,4 butanediol mixture to soy oil is about 1.50:1. The A-sidecomprises a 2,4′ rich polymeric MDI, Mondur® MRS-20, and was reacted at70 parts to 100 parts B-side. The resulting reaction had no foaming andno real reaction.

Example 25

Example 24 is repeated with A-side comprising Mondur®-PF, a modifiedMDI. Again, no foaming and not a good reaction.

Example 26

Example 24 is again repeated, with the A-side this time comprising a50/50 mixture of a modified MDI, MA-2901, and a modified pMDI, Mondur®448. It is reacted at 70 parts to 100 parts B-side.

Example 27

The A-side comprises a modified MDI, MA-2901. The B-side comprises thefollowing:

B-side 100 g Soy Oil 7 g Dipropylene-glycol (cross-linker) 2 g Front endcatalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropyleneglycol) 2 g Back end catalyst (DABCO ® 8154; an amine salt)

The A-side and B-side reactions were mixed in a ratio of 60 parts A-sideto 100 parts B-side. The resultant foam exhibited excellent properties.

Example 28

B-side 100 g Soy Oil 3 g Dipropylene glycol (cross-linker) 2 gSurfactant 2 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamineand 67% dipropylene glycol) 2 g Back end catalyst (DABCO ® 8154; anamine salt)

The A-side and B-side reactions were mixed in a ratio of 60 parts A-sideto 100 parts B-side. The resultant reaction produced a foam exhibitingexcellent properties.

Example 29

The A-side and B-side components are identical to those in Example 28.The A-side was reacted with the B-side in a ratio of 68 parts A-side and100 parts B-side. Once again, the foam produced by the reaction hadexcellent properties.

Example 30

The A-side comprises a mix of a modified MDI, MA-2901, and a modifiedpMDI, Mondur® 448. The B-side comprises the following:

B-side 100 g Soy Oil 3 g Tripropylene glycol (cross-linker) 3 gDipropylene glycol (cross-linker) 2 g Front end catalyst (DABCO 33-LV ®;33% triethylenediamine and 67% dipropylene glycol) 2 g Back end catalyst(DABCO ® 8154; an amine salt)

The A-side and B-side were mixed in a ratio of 60 parts A-side to 100parts B-side. The resultant foam was a rigid foam exhibiting excellentproperties.

Example 31

In this example, the A-side was identical to the A-side of Example 30and the B-side is identical to Example 30 except for the fact that 6%butanediol was added to the B-side. The A-side and B-side were mixed ina ratio of 60 parts A-side to 100 parts B-side. The resultant foam was arigid foam exhibiting excellent properties. The addition of thebutanediol increased the speed of the reaction compared to Example 30.

Example 32

The A-side comprises polymeric MDI. The B-side comprises the following:

B-side 200 g Soy Oil 30 g Ethylene glycol (cross-linker) 15 g Butanediol(cross-linker) 5 g Aliphatic amine tetrol (CL-485; cross-linker) 25 gMolecular sieve (L-paste ™) 8 g Front end catalyst (DABCO 33 LV ®; 33%triethylenediamine and 67% dipropylene glycol) 5 g Back end catalyst(DABCO ® 1854; an amine salt)

The A-side and B-side were mixed in a 1:1 ratio. The foam resulting fromthe chemical reaction was a rigid foam with good properties.

Example 33

B-side 100 g Soy Oil 10 g Butanediol (cross-linker) 6.4 g Ethyleneglycol (cross-linker) 3 g Aliphatic amine tetrol (cross-linker) 3.2 gFront end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67%dipropylene glycol) 3.0 g Back end catalyst (DABCO ® 1854; an aminesalt) 5% Molecular sieve (L-paste ™)

The A-side and B-side were mixed in a ratio of 35 parts A-side to 100parts B-side. The resulting foam was very good after about 15 minutes.

Example 34

The A-side comprises either MDI or pMDI. The B-side comprised thefollowing:

B-side 200 g Soy Oil 200 g Polyurea polyol 48 g Aliphatic amine tetrol(cross-linker) 30 g Ethylene glycol (cross-linker) 3 g Front endcatalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropyleneglycol) 3 g Back end catalyst (Polycat 41 ®; n, n′, n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 3 g Tertiaryamine catalyst (DABCO ® BL-22) 7 g Molecular sieve (L-paste ™)

The A-side and B-side were combined in a ratio of 50 parts A-side to 100parts B-side. The result reaction occurred very fast and the resultantelastomer exhibited good properties. Combining the A-side and the B-sidein a ratio of 68 parts A-side to 100 parts B-side also results in anelastomer with good properties.

Example 35

B-side 300 g Soy Oil 300 g Polyurea polyol (petroleum based polyol) 33 gButanediol (cross-linker) 11.3 g Front end catalyst (DABCO 33-LV ®; 33%triethylenediamine and 67% dipropylene glycol) 7.6 g Back end catalyst(Polycat ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazinetertiary amine 5 g Aliphatic amine tetrol (DABCO ® CL-485; cross-linker)

The A-side was blended with the B-side in a ratio of 40 parts A-side to100 parts B-side. The resultant foam had good properties, but wasslightly hard.

Example 36

The A-side and B-side are identical to Example 35, however, 5% methylenechloride and 1% of a stabilizing anti-oxidant, Stabaxol® were added tothe B-side. The A-side and the B-side were mixed in a ratio of 32 partsA-side to 100 parts B-side and a ratio of 36.5 parts A-side to 100 partsB-side. Both resulting foams were good, soft foams. The addition of themethylene chloride as a blowing agent greatly assisted the reactionwithout pulling out water thereby allowing the foam to stay soft.

Example 37

The A-side comprises a 50/50 mixture of modified MDI and modified pMDI.The B-side comprises the following:

B-side 400 g Soy Oil 400 g Polyurea polyol (petroleum based polyol) 96 gAliphatic amine tetrol (cross-linker; amine salt) 60 g Ethylene glycol(cross-linker) 6 g Front end catalyst (DABCO 33-LV ®; 33%triethylenediamine and 67% dipropylene glycol) 3 g Back end catalyst(tertiary amine catalyst) 6 g Blow catalyst (DABCO ® BL-22)

The A-side was combined with the B-side in a ratio of 50 parts A-side to100 parts B-side. The resultant foam exhibited good overall properties.

Example 38

The A-side comprises a polymeric MDI, Mondur® MR light. The B-sidecomprises the following:

B-side 50 g Soy Oil 50 g Sucrose polyol (Bayer 4035) 10 g Ethyleneglycol (cross-linker) 2.5 g Dipropylene glycol (cross-linker) 3.0 gFront end catalyst 2.0 g Back end catalyst (tertiary block aminecatalyst)

The A-side was mixed with the B-side at the following ratios:

A-side B-side 50 100 70 100 80 100 90 100 100  100

Each mix ratio resulted in a very fast reacting high-density foamexhibiting good qualities overall.

The above description is considered that of the preferred embodimentsonly. Modifications of the invention will occur to those skilled in theart and to those who make or use the invention. Therefore, it isunderstood that the embodiments shown in the drawings and describedabove are merely for illustrative purposes and not intended to limit thescope of the invention, which is defined by the following claims asinterpreted according to the principles of patent law, including thedoctrine of equivalents.

1. A material comprising the reactive product of an A-side comprising aprepolymer diisocyanate and a B-side comprising a first blown vegetableoil, a cross-linking agent comprised of a multi-functional alcohol and acatalyst, wherein the first blown vegetable oil and the cross-linkingagent are substantially non-esterified prior to the A-side reacting withthe B-side.
 2. A method of preparing a material comprising the steps ofcombining an A-side material comprising a prepolymer diisocyanate with aB-side comprising a first blown vegetable oil, a cross-linking agentcomprised of a multi-functional alcohol and a catalyst, wherein thefirst blown vegetable oil and the cross-linking agent are substantiallynon-esterified prior to combining the A-side with the B-side.
 3. Amaterial comprising the reactive product of an A-side comprising aprepolymer isocyanate and a B-side comprising a first blown vegetableoil, a cross-linking agent comprised of a multi-functional alcohol and acatalyst, wherein the first blown vegetable oil and the cross-linkingagent are substantially non-esterified prior to the A-side reacting withthe B-side.
 4. A method of preparing a material comprising the steps ofcombining an A-side material comprising with a B-side material, whereinsaid A-side comprises a prepolymer isocyanate and a B-side wherein theB-side comprises a first blown vegetable oil, a cross-linking agentcomprised of a multi-functional alcohol, a catalyst, and a blowingagent, wherein the first blown vegetable oil and the cross-linking agentare substantially non-esterified prior to combining the A-side with theB-side.